Method and apparatus for catalytic conversions



July 25,` 1944. A. 3. ABRAMs METHOD AND APPARATUS CATALY-TIC CONVERSIONS Filed Jam. 4, 1941 4 Sheets-Sheet 2 /za/r @PAV/W Maf 4. .,IQ /f P J 7 M 5.3 0 2 M, i fv w M 7 n /x f w All A n r, n A 00 L f. P MJ., M Y 5 MMM um, W www W W @www W; w m m A U 6M 76M 6 6 G m r c an H N H cw E 5 L H INVENTOR zmo/xaj/@zg/y;

July 25, 1944- A. J. ABRAMs 2,354,353

' METHOD AND APPARATUS FOR GATALYTIC coNvER'sIoNs K Filed Jan. 4, 1941 v4 sheets-sheet s-` HMTGAS voar OW @AMV/Tx M227 0W GRAVI TY IIIHH.

INVENTOR 4 Sheets-Sheet 4 INVEN-roR RG 0N v. W NalnN T ,M /,Mm WT WT 0M A. AL FL 7 W W RE 6 E EU MM M @n.64 w. M

METI-Io AND APPARATUS FOR GATALYTIC coNvERsIoNs OWG/PAW MEL 7` UP -I @a4/vo J (dau/7J' 'BYv v A oRNEY July 25, 1944.

6,45 Ta @E T/PEA TED, /Nm 6,45 /lv 00m/v6 ,4er/v4 770A( siderable complexity.

Patented 1.944

snrrnon Nn '2,354,353 mana'rt'r's Fon cs'rannrc coNvsnsIoNs Arianna Linfoma, Tex., assimito Sonny-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New York Appuoouon January 4, 1941, sonal No. :13,1175

'19 Claims. Numerous processes'and apparatus setups have been proposed for the accomplishment of cata-l lytic conversions of various materials inthe ,valv

por phase in the presence of a contact mass. One group of these processes and apparatus setups has to do with conversions wherein the material to be converted is contacted in the presence of some iluld, such as a molten metal, which itself may 'in some cases be a catalyst for the reaction, in the presence of contact bodies or spreading bodies, which bodies may be and usually are lcatalytic to the conversion. This lx1-'- vention has broadly todo with 'conversion proc esses of this general type.

In conversion processes 'of this general type1 used heretofore there are involved equipment setups in which heat is transferred through a coniining wall, either to the catalytic material, or to the material to 'be' treated, or to both.

l This general practice oi heat transmission through a cog wall, either to' vput heat` into the zone vcontainingthe catalytic bodies asis the case in endothermic reactions or to remove heat' from said zone as in the case in exothermic re" actions, entails problems of heat exchange and of temperature control, the'solution of'whlch selves readily to adaptation for use with catalytic masses.

This invention has for its principal 'object the provision of catalytic vapor phase 'conversion methods wherein. conversion is accomplished by flowing reactants in contact with spreading material, which may be catalytic, and in contact with a heated liquid, whichI may be catalytic, in-

which heat control and transfer-iis effected-by' 'processes involving physical contact of heat ply media, heat transfer media, and heated media.- i It has as a further object the 'povisioxiofcat--v alytic vapor. phase processes as described wherein provisions for regeneration'of spreadingl or solid contact material and regeneration of' fluid generally has involved special l'appitratusde-v signs and temperature control methods' -ot con- In ddltion it should be considered that this general'practice of heat transfer through a con`- lining wall, puts severe limitations `on the 'temperature at which such catalytic reactions can" be carried out, either on account of the 'cost of stru'ctural materials or o n account of the second-` ary reactions induced by them at temperatures above those now used commercially. It is well v known, 'forinstance, that there are a number of refractory oxide catalysts and othersimilarinorganic catalysts for reactions of immediate importance to the petroleum industry, which do' not sinter, at temperatures well above those to which their use is restricted at present because of temperature limitations in materials of'con-f struction'both as to strength and vas to cost.

These limitations are real drawbacks-which aifect-l considerably a more general commercial development of .uses for the immense supplies oi meth#- v ane, -ethane and propane.

Schemes in which in one cycle heat is imparted ,to s large continuous or discontinuous reirsetory heat storing mass, which heat is then for treatment of the hydrocarbon iiuid in ani other cycle'bytreating in the-presence' oi this -saine heatcontaining mass, do not lend thln- 55 contact material are each conducted under optimum conditions. Ithas as afurther .object the provision of catalytic vapor phase processes' as described, ywherein heat 'is supplied or removed fror'n the reaction without the use of heat rcgenerators and without passing" such' heat through a confining wall. A further object isthe provision of apparatus appropriatefor such-I processes.

'This invention is based upon the .concept of method and apparatus wherein a material inthe vapor `phase is catalytically converted' while flowing through a packed conversion zone, the' packe" ing of which may or may not be catalytic tothe reaction, in the presence of a molten heat trans' fer material, which may or may not be catalytic to the reaction, which molten material iiows, un' der non-ooding conditions, over the packing material without appreciably wettin'g it, and. which molten material is onev of a combinations! 'two used 'as heat? essentially dissimilar molten liquids transfer media.

Tho invention is useful in oonrioouon Awith any' catalytic `vapor phase conversion process, but' since it appears most highly use'fulwith hydro,-

ca'rbon conversions, it will beidiscussed in connection therewith, without being limited thereto'.

In the. ileld of hydrocarbon conversion it is ape plicable to a large number of catalyticconversion problems, such ascatalytic cracking. de'

hydrogenation. cyclization, aromatization, poly merixation, isomerization, alkylation and the v by the use or a' combination of moin and cata-"- lyst bodies particularly suited for the lar conversion problem at hand.

- Molten liquids in contact with com catalysts were either suspended or dhsolved in the molten' medium. This is van all importait ai.' y been proposed before but in all cases known'the which 9, is a heat exchange zone.

diierence insofar that this process is operated under non-flooding conditions in which the solid catalyst is not appreciably wetted bythe molten heat transfer medium and in which the catalyst therefore is able to function under entirely different conditions than in theprocesses above referred to. In some proposed processes,y packed towers have been recommended for use in the treatment of hydrocarbons in the presence of molten materials but not in the presence of paokings which had definite and appreciable catalytic properties and were used for an express catalytic purpose. Apparently no cases are on record of the use of inorganic melts or molten metals to convey heat directlyto a packed tower environment containing an active catalyst compounded of various inorganic ingredients such as mixtures of oxides or sulfides, etc. n the contrary the belief seems to be held pretty generally that if leakage occurs in a catalytic converter from the heat transfer medium side to the section cone taining the catalyst, the catalyst efilciency is quickly destroyed or at least seriously impaired; To avoid such an outcome, engineering design studies have usually culminated in apparatus of considerable complexity.

'I'he invention may be readily understood by reference to the drawings attached hereto, the four figures of which show several modifications of the process and apparatus of this invention, all in diagrammatic form. 4

Before discussing any of the figures, it may be helpful to restate the principle of operation, in which vaporous or gaseous materials, hereinafter spoken of as hydrocarbons, pass through a packed tower in contact with a molten material such as lead. The packing may be and preferably is catalytic to the reactiondesired. The molten lead is passed through the tower in such `quantities that it brings to the zone oi reaction sufiicient heat to accomplish the reaction, but in amounts insufficient to flood the tower. Outside the tower, the molten lead eiliuent therefrom is reheated by physical contact with a second hot' molten fluid, such as, for example, a molten 'inorganic salt, which is immiscible with and of lower these from the high gravitymelt. the low gravity `melt is introduced to space Il by pipe I2 and spreader I9, and in passing up through the heavyI melt, the light melt scrubs the carbonaceous material therefrom, collecting itat I I. The light melt charged with this carbonaceous material is then removed from space I4 by pump 25, and is passed into regenerator 5 byv pipe 2|. Regenerator 5 has a packing of inert materiaLpreferably a refractory, at 22. The light melt nows therein ccuntercurrent to an oxidizing gas. in

. vtroduced, at 23 and removed at 2|. and is freed .of carbon and like impurities, returning to use by pipe 25. In order to supply heat for the process, the heavy melt is removed from space Il by pump 21 and sent by means of pipe 28 to vessel same character as the first low gravity melt used in vessels 5 and 5', this second low gravity melt may be different in character, since the two circuits do not intercommunicate. In 5, the lower part'of vessel 1, there is an inert, refractory packing 25, supported by 25. High gravity melt trom pipe 28 iiows downward through this packing. I-Iot low gravity melt from seal 24 is introduced at I1, below the packing and flows upward therethrough, heating the high gravity melt during its physical contact therewith. High gravity melt, now reheated,'is withdrawn through seals and returned to vessels I or 5'. Low gravity melt collects at 25 and is recirculated by pump 40.

The high gravity melt used is a molten metal or molten alloy of'low melting point, non-reactive specific gravity than the lead. This s'alt is in turn heated by physical contact with gases of combustion.

lirning now to Figure 1, we iind vessels 5 and 5', which are catalytic converters, vessel l which is a melt regenerator, and vessel 1, the upper part of which, 8, is a melt-heater and the lower part of Vessels 5 and 5 are identically equipped with a packed zone, III-III', containing a packing of contact mate# rial catalytic to the desired reaction, supported by a screen or grid II--I I', below which there is a space I2 for separation of the two immiscible molten materials, the high gravity melt collecting at the bottom, I3, and the low gravity material collecting thereabove at il. During reaction, vaporous hydrocarbons are introduced at Il and reaction products are withdrawn at I5. During regeneration of the catalytic packing Il, meneration medium is introduced at Il and regeneration products are withdrawn at I5.- Durwith the catalytic packing material and not capable of appreciably wetting it. This melt may be catalytic in the reaction being carried out, if desired. Many metals and` alloys may be used, and of these lead is typical.

The low gravity melt must be resistant to oxidation, of different speciilc gravity from thehigh gravity melt, and not miscible therewith. Many materials, such as molten inorganic salts. may be 'used for certain dehydrogenation reactions.

Turning back toFlgure .1, it will be noted that the provision of two reaction vessels namely l and ing reaction, the high gravity melt, lead. is introat thebottom of vessel'l. In the .conversion, the high gravity melt picks up carbon and materials from the reaction. To remove I permits of regenerating one vessel while the other is operating upon reaction.

It 4is understood um at the beginning of the v operation the mem used may be introduced at such points as 4I and I2 shown in Figure 1 or other convenient points not shown.- 'I'he melts or molten lead are preheated in one of several standard melting furnaces available for this purpose. vAt shutdowns the .various melts would be returned yby drainage or otherwise to their re' spective storage points, vis., melting pots, through returned through v)pipe IB.

assasss lines and valves Il and n or other convenient exit points not shown. It is also understood that lthe necessary transferiines will be so heated as to prevent solidiilcation of the molten fluids circulating therein. l i

The set-up shown in Figure 1 is one which is I applicable when the process or choice of low gravity melts is such that it is inadvisable to use the same low gravity melt for carbonremoval in vessels! and I' and forfheat storage in vessel 1. .When the same low gravity melt may be used for both purposes, a simpler arrangement may beutilized,asshowninFigureII. InthisFlgure II, vessels I, I', and 1 are arranged and equipped exactly as theyv were in Figure I. Vessel 'I of Figure I is omitted. In Figure II low gravity ity melt. As before, the low gravity melt and' high gravity melt interchange heat in I and reheated high gravity melt departs through pipes l1 to vessels I or I'. Low gravity melt is returned from I to spreaders il by pipe 4I. '5

' In certain cases it is advantageous to remove carbon from the low gravity melt simultaneously with the regeneration of the catalytic packing material in vessels I or I'. A convenient modification for this purpose is shown in Figure III; In Figure III, vesselsv I, I', and 1 are the same low gravity melt M accomplishes both the more important purpose of heat transfer and the secondary purpose of carbon scrubbing. During this period I' has been regenerating. When I' is placed -upon reaction,

the ilow is correspondingly changed. High gravvity melt will now through Il', si', Il, Il', I2', and through Il', Il, II, I, Il'. Il',

Il and Il'.

It may be noted by comparison'of these figures that all embody the basic principle of transferring heat into the reaction by physical' contact, first between a hot gas and a low gravity melt,

. second by contact ofthe low Agravity nelt with a high gravitymelt, and third by contact of the melt from space Il of vessel I is passed by pipes high gravity melt and the reactant. All of thesetransfers are of a type high in relatiye'emciencg and entirely without the presence of limits im,-

posed'by enveloping or interventing materials'of construction.

. In its essentials, the conceptof this process involves several operations, as detailed below.

Circumstances permitting, some. of these operai,

tions may be combined, as pointed outfi'n previ-l ous discussion. .A (1) Transfer of heat from a gas to a meitgby i physical contact'.

as before and with minor exceptions, equipped the same as before. The arrangements for heating high gravity melt in vessel 1-and recirculating it are the same as before. Only the 16W gravity melt circuit around vessel I is changed. vIn this Figure III low gravity. melt is removed from` spaces Il by pump II and is returned by pipes 41- to flow over the packing material in vessels I or I. An intercommunicating pipe 4I is proin Figures I and II are dispensed with, since the` heavy melt can be scrubbed in its downward passage through the space il in the vessel which is on reaction. l

In Figure IV a still more simplified setup is shown, applicable to situations such as in Figure III. Here vessels I and I' are in general character and fittings the same as in previous ngure's, but of vessel 'I only the heating section I is retained. Assumingthelefthandvesselltobe ony reaction and the right hand vessel I' to beA on regeneration, operation will be as follows: High gravity melt will be removed from space II by pipe sl and pump sito pass through pipes Il and ,I2 to the top of I, wherein it passes down through the tower, giving up heat to the reaction and otherwise acting as before, and collects in II at the bottom of I. Low gravity melt is removedfromil by. pipe Il and pump Il to flow through pipe II into heating section I and is returned therefrom, after belngheated and freed of suspended carbon, as in Figure II, by Dive II and introduced into II by spreader Il. The intimate'contact ofthe two melts in spaces II and `(2) mugre: of heat from 'the om inem to a' second melt by physical contact.

(3) Separation of the-melts by utilization of differences in specific gravity.

(4) Conversion of vvapor-ous reactants'f'l in passage over a suitable contact mass in the" presence of the second melt as a heat transfer agent. this second melt being one which does not appreciablywet the contact mass, and being present in quantities insuillcient to flood the conversion zone.

(5) Use of melts to remove entrainefd carbon and other solid or liquid products produced in the reaction zone and transferi them into an oxidizing zone. j

(6) -Oxidation of the carbon, etc., fromthe melt in an oxidizing zone.

(7) Regeneration of the contact mass in situ by means of an oxidizing gas.

'I'he process may be used, f or example.. for such reactions as the dehydrogenation of propane to propylene using as contact mass an AlzOs-CrzO: catalyst in the presence of molten lead as' a heavy melt. Below are shown the results di several.`

experiments. In some of thesel experiments the' catalyst was composed of pellets of activated alumina impregnated with a solutionof chromic acid and dried. In others, the catalyst' was pre,

pared by co-precipitating aluminum and chro-l mium'hydroxides from solutions ofthe' nitrates Per dem?.l ,j Table I Y Space velocity A s s 11.2 12 14 1s 22:',V

Volume gromt prol. pylsns exit gas-.-

. noleld 40.5 16.5 19.9 11.0 18.8 14.9 13.4

ene pas- Iwith lead 16. 0 17.15 19. 9 19. I 17. 7 16. 2 III Temperature 650 C. n i

The above experiments were-run to dete the optimum space-velocity (volumes of 'gas reacts'nt per volume of catalyst per u'nit of time, in Athis' case cubic centimeters ditlons) per cubic centimeter per minute) for m.- sandaru ccnl-i sluier operation.' wnne the' best space velocity for both appears to be at about 11 to 12, note that the sensitivity -of the reaction with leadis` less pronounced. i

- Table 1I A-witheueieae n-witn les Temperatura 550' C. Space velocity 14 i vol.

pylenoin -Runningthna minutes exit f v s a 4o r1.2l is. m 11.s V1a iso. 11.: da no l 16.0 '11.

Note the improved for conversion. in

. the presence ofthe highA gravity melt, lead, other conditions being-the same. l

In both of these experiments the co-precipitated type'ofcatalystwasutilized. s A third set offexperimentswas carried out to' demonstrate that the regeneration'of the catalyst in the presence of lead was without'harmiul eiiect upon the reaction.,. The general procedure was to carry out` reaction -ior two hours, during which time sampleaweretaken at convenient" intervals. The catalyst wasthen regenerated with an oxidizing gas. a mixture of oxygen and nitrogen, andv the cycle repeated.- lable III shows exemplary results, taken at'comparative points well into the ,A ver! important advantage of the process' ammessi situ comprising passing the hydrocarbons in vapor iorm and at conversion temperature through said contact mass, additionally ilowing over said contact mass a high gravityfluld heat transfer medium selected from the v.group vmetals and 'metal alloys. in molten form, said fluid medium being present in amount insuillcient tol flood the interatices of the contact massfsald fluidmedlum being incapable or vapprei'ziahlvwetting said contact mass. contacting said high gravity fluid medium at a point external tosa'idfcontact mass with a low gravity duid from -the group l molten inorganic salts and mixhires of inorganic .salts inert to'oxidation.- heating said low gravity sum prior to 'eonmt'witnfmgh gravity aum by a physical contact of low gravity duid and hot gases,

periodically* stopping flow of. hydrocarbons and high gravity duid throughsaid contactmass. passing regenerationgascs therethrough and returning the regeneratedcontact lmass to'servicc 2. The processo! claim 1 in whlch. during re- '.generation of the contact mass. the lowgravity fluid heat transfer medium -is flowedover said ,contact mass during the-passage of regenerating gases therethrough.`

3. A process for the conversion o! hydrocarbons in thepresence of s.V contact mass comprising passing the .hydrocarbons in vapgr'fcrm'and at conversion temperature through said contact mass.,additionally,flowingover,l said contact mass a high gravity fluidheat transfer medium selected from the group metals and metal alloys. in molten y form, said fluid medium being present lri amount insuilicient to flood the intcrstices of the contact u mass, said fluid medlumhelng incapable of apherein disclosed from its ability; as shown.' to avoid the economic and physical limitations laid upon other processes because-oi their necessity for reliance upon heat transferred through a confining wall of some variety. which heat m in turn he` transferred vthrough catalysts -iusu of 'catalyat'not in contact withthe connnin'g wall. That necessityyis `herein avoided vby complishing-heat transfer by physical contact.

.An additional advantage arises vfrom the action of the various meltsfin decreasing the amount of material deposited upon the contact mass. thus y Y ahility'to maintain reaction at an economic-level oiconversiomfor a longer period of time.

I`\claim: v 1. A unitaryprocess for the conversion of hydrccarbonswin the presence of a contact followed `hyregcneration ofthe contact mass lleading tohi'gher ratea of conversion and/ or preciably wetting said said high gravity .fluid medium at a point external to said contact mass with a low gravity duid medium selected from the group molten inorganic salts and mixtures of inorganic salts inert to oxidation for removal of carbonaceous matter from the high gravity liquid, circulating sald'low gravity fluid medium into contact with an oxidizing gas at a point external to its vcontact with heavy fluid medium and external to the reaction contact mass for removal of said carbonaceous matter from' the low gravity liquid and returning 'auch low lgravity liquid to contact'with'thehigh gravity liquid, circulating the high gravity fluid Y medium to a point external to the reaction contact mass and there contacting the high gravity fluid medium with a second low gravity uld medium. to adiust .the temperature of the high gravity fluid medium and returning the high gravity fluid medium to the reaction contact mass.

Apparatus for the conduct of hy eonversioninthe presenceof acontact maas comprising-areactionvesseiacontactmassinsuch vesseLinletandexitmeanstopasshydrocarbon reactants and regeneration medium alternately therethrough. inlet andexit meansto fluid heat'exchange medium over said contact mass in physical contact therewitmliquiddiduid mixingmeans-whereby gaidrs't fluid heat ex-l changeniediumxnayheintimatelyifliillilml a second fluid heat -exchangenmedium imm .the in cameramanmaquis soatact vessel visolated from the reactionvessel. inlet and exit means to duid heat exchange medium therethrough. lconduits leadim the second fluid from the 'gas-liquid contact vessel to the liquid-liquid mixing'means and fmm'the liquid-liquid mixing to the gas-liquid contact. and

inlet andexit meanswherebyaheatedgalmay ih u: ipe-ies through ene' ges-umd manueel.

tact mass, contacting 5. Apparatus for the conducto! hydrocarbon .conversion in the presence of a'contact mass comprising a reaction vessel, a contact mass in such vessel, inlet and exit means to pass hydrocarbon reactants and regeneration medium alternately therethrough, inlet and exit means to pass a first fluid heat vexchange medium over said' contact mass in physical contact therewith, liquid-liquid mixing means whereby said rst i'iuid heat exchange medium may be intimately contacted with a second fluid heat exchange medium differing from the first in specific gravity, a gas-liquid contact vessel isolated from the reaction vessel, inlet and exit means to pass the second fluid heat exchange medium therethrough, conduits leading the second fluid from the gasliquid contact vessel tothe liquid-liquid mixing means and from the liquid-liquid mixing to the gas-liquid contact, and inlet and exit means whereby a heated gas may be led through the gasiquid contact vessel and in addition thereto, a heating zone external to the reaction vessel in which comprises passing the hydrocarbons in a gaseous state under conversion conditionsA4 tion resistant liquid medium, and then returnwhich heat may be supplied to the flrst named fluid heat exchange medium, said heating zone being provided with pipe means whereby said first named fluid may be circulated between the reaction vessel and the heating zone. v

6. A process for the conversion of hydrocarbons in the presence of a contact mass which comprises passing the hydrocarbons in gaseous form and under conversion conditions through said contact mass, additionally flowing over said contact mass a high gravity liquid heat transfer medium selected from the group consisting of molten metals and metal alloys, said liquid medium being present in amount insufficient to ilood'the voids of the contact massv and said liquid medium being incapable of appreciably wetting said contact mass, contacting said high gravity medium at a point external to said con' tact mass with a low gravity liquid medium se-i lected from the group consisting of molten in organic salts and mixtures of inorganic salts inert to oxidation, heating said low gravity liquid prior to contact with saidV high gravity liquid by a physical contact of such low gravity liquid with a gaseous medium, and returning said high gravity liquid after contact with said low gravity liquid to said contact mass.

7. The process of claim 6, wherein the contact mass comprises a catalyst for effecting said con-,- version reaction.

8. Apparatus for conducting hydrocarbon conversion in the presence of a catalytic contact mass comprising a plurality of reaction vessels, a catalytic contact mass in each of such vessels, inlet land exit means provided in each of such vessels for passing hydrocarbon reactants and reing the reconditioned liquid heat transfer medium to the conversion zone.

10. The process of converting hydrocarbons which comprises passing the hydrocarbons in a gaseous state under vconversion conditions through a conversion zone, flowing a liquid heat transferring medium of highl gravity through said zone in direct contact with said hydrocarbons whereby heat is transferred to the hydrocarbons and carbonaceous residue produced as a by-product of the conversion is carried alongin the liquidmedium,rremoving liquid heat transfer 4medium from'the conversion zone, scrubbing the removed medium in a scrubbing zone with a low gravity liquid medium which is immiscible with the high gravity medium and which is not sensitive to oxygen under combustion conditions thereby transferring the carbonaceousresidue to the low gravity medium,- directly contacting said removed high gravity medium with a vheated liquid medium of low gravity and which is im# miscibie therewith to adjust lthe heat content of such high gravity medium for re-use in the conversion zone, and returning this heated, essentially carbon-free high gravity medium to the conversion zone. y

ll. The process of converting 'hydrocarbons which comprises passing the hydrocarbons in a gaseous state under conversion conditions through a conversion zone containing a bed of contact material, flowing a liquid heat trans--l ferring medium of high gravity through said zone in direct contact with said hydrocarbons but in insufficient amount to Aflood the voids of the bed whereby heat is transferred to the hydrocarbons and carbona'ceous residue produced generation medium alternately through 'each of such vessels, inlet land exitmeans in each of such vessels for passing a liquid heat exchange medium through said vessels in physical contact with the contact mass therein, liquid-liquid mixing means wherein a relatively high gravity liquid heat exchange medium may be intimately contacted with a relatively low gravity heat exchange medium,

means for passing high gravity liquid from said liquid-liquid mixing means selectively to each oi' said vessels, means for passing said low gravity liquid from said liquid-liquid mixing means selectively to each of said vessels, and means for passing liquid heat exchange medium from each of said vessels to said liquid-liquid mixing means.

9. The process of converting hydrocarbons as a by-product of the conversion is carried along in the liquid medium, removing liquid heat transfer medium from the conversion zone, scrubbing the removed medium in ascrubbing zone with a low gravity liquid medium which is irnmiscible with the high gravity medium andwhich is not I sentitive to oxygen under combustion conditions thereby transferring the carbonaceous residueto the low gravity medium, directly contacting said removed high gravity medium with a'heated liquid` medium oi' low gravity and which is immiscible therewith to adjust the heat content o f such high gravity medium forre-use in the conversion zone, and returning this heated high Y gravity medium to the conversion zone'.

12. The process of claim lowherein said contact material comprises a catalyst for effecting said conversion.

13. The process of claim 6 in which the gaseous medium contacted with the low gravity liquid is a combustion supporting gas whereby at least l l part of the heat supplied to heat the low gravity liquid will be supplied by the combustion of any combustible impurities in the low gravity liquid.

`14. A process for the conversion of hydrocarbons which comprises'passing'the hydrocarbons in a gaseous state under conversion conditions through a conversion zone containing a catalyti- 6 assists cally active contact mass for effecting said conversion, additionally flowing over said contact mass a high gravity liquid heat tranfer medium selected from the group consisting of molten metal and metal alloys at a rate insuflicient to f ilood the voids of said contact mass, said liquid medium being incapable of appreciably wetting ,said contact mass, whereby heat is transferred to. the hydrocarbons and carbonaceous residue profl molten inorganic vsalts and mixtures of salts inert to oxidation thereby transferring the carbonaceousresidue to the low gravity liquid, heating low gravity liquid which has previously been con tacted with said high gravity liquid prior t its further contact with said high gravity liquid with a combustion supporting gas whereby at least part of the necessary heat will be furnished by combustion of the carbonaceous residue, and returning said-high gravity liquid, after contact i with said low gravity liquid to said contact mass.

15. A process for the conversion of hydrocarbons which comprises passing the hydrocarbons` in a gaseous state under conversion conditions through a conversion zone containing a contact mass for veffecting said conversion, additionally flowing over`said contact mass a high gravity to flood the voids of said contact mass, said liquid medium being incapable of appreciably wetting salts and mixtures of 'salts inert to oxidation, contacting the low gravity liquid medium with an oxidizing gas under combustion conditions to remove the carbonaceous residue from the low gravity liquid. reh'eating the high gravityliquid -by directly contacting it with a low gravity liquid medium immiscible therewith and returning saidhigh gravity liquid to said conversion sone.

16. The process of conducting a Wroleulc reaction which comprises passing a volatilizable organic compound in a gaseous state under conversion conditions through a conversion zone containing a bed of contact material, flowing a liquid heat transfer medium through said none lin direct contact with said'organic compound,

removing liquid `heat transfer medium from said zone and reconditioning it -for reuse in the conversion zone by direct contact with at least one other inorganic, oxidation resistant liquid inedium, and then returning the reconditioned liquid heat transfer medium to the conversion zone.

17. The process of conducting a PYIOBenic reaction which comprises passing a volatilizable organic compound in a gaseous state under conversion conditions through a conversion zone containing a bed of contact material, flowing a liquid f heat transfer medium through said zone in direct contact with said organic compound but in insufficient amount to flood the voids of the bed.

' liquid heat transfer medium at a rate insumcient removing liquid heat transfer medium from said zone and reconditioning it for reuse in the conversion zone by direct contact with at least one other inorganic, oxidation resistant liquid medium, and then returning the reconditioned liquid v heat transfer medium to the conversion sone.

18. The process of claim 16 wherein said oontact material comprises a catalyst for effecting said conversion reaction.

. 19. Apparatus for conducting pYrOenic reactions involving volatilizable organic compounds in the presence of a contact mass comprising a reaction vessel, a contact mass in such vessel, inlet and exit means to pass the organic reactant in the vapor state through said reaction vessel, inlet and exit means to pass a first fluid heat exchange medium through said reaction vessel and over and in physical contact with the contact mass therein. liquid-liquid mixing means connected to said last mentioned inlet and exit means wherein said iirst fluid heat exchange, medium may be intimately contacted with a lsecond fluid heat exchange medium diifering inspecinc gravity from Athe rst, inlet and exit means in said liquid-liquid mixing means to permit the entry and exit of the second duid medium, and means to maintain the temperature level of said second iluid.

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